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Energies 2019, 12, 809 15 of 41 Energies 2019, 12, x FOR PEER REVIEW 16 of 42 4. Catalytic Upgrading of Sugars, Starches and Alcohols 4. Catalytic Upgrading of Sugars, Starches and Alcohols Since 2006 Virent Energy Systems Inc. (Madison, WI, USA) has developed a platform of processes Since 2006 Virent Energy Systems Inc. (Madison, WI, USA) has developed a platform of for the conversion of carbohydrates into liquid fuels like green gasoline, green jet fuel and green diesel, processes for the conversion of carbohydrates into liquid fuels like green gasoline, green jet fuel and as shown in Figure 4 [120]. green diesel, as shown in Figure 4 [120]. ® FFiigguurree44. .Virireennt’ts'sBBioioFFoorrmiing®pplalatftoforrmfoforrththeepprorodduucctitoionnooffrerenneewaabbleletrtraannssppoorrttaattioionnffuueelslsfrfroom bbioiomaasssfefeeddsstotocckkss[1[12200].].Reepprroodduucceeddwitihthppeerrmisissioionnfrfroom[1[12200].].Virierennt:t:CCooppyyrrigighhtt2200088. . The platform is known as BioForming® and involves liquid phase technologies such as The platform is known as BioForming® and involves liquid phase technologies such as hydrolysis, hydrogenation, hydrogenolysis, dehydration, isomerization, oxidation, aqueous phase hydrolysis, hydrogenation, hydrogenolysis, dehydration, isomerization, oxidation, aqueous phase reforming (APR) and aldol condensation [121–125]. Biomass (lignocellulosic, sugars, starches) is reforming (APR) and aldol condensation [121–125]. Biomass (lignocellulosic, sugars, starches) is initially pretreated with dilute sulfuric acid catalyst (0–3 wt%) at about 130–220 ◦C for 2–30 min. initially pretreated with dilute sulfuric acid catalyst (0–3 wt%) at about 130–220 °C for 2–30 min. This This breaks down the biomass for a subsequent enzymatic hydrolysis with the cellulase enzyme which breaks down the biomass for a subsequent enzymatic hydrolysis with the cellulase enzyme which converts polysaccharides like cellulose, hemicellulose, starch and inulin into a hydrolysate slurry of converts polysaccharides like cellulose, hemicellulose, starch and inulin into a hydrolysate slurry of monosaccharides such as xylose, fructose and glucose. The slurry is then purified from insoluble solids, monosaccharides such as xylose, fructose and glucose. The slurry is then purified from insoluble proteins and inorganic compounds which are problematic for the operation of the plant equipment solids, proteins and inorganic compounds which are problematic for the operation of the plant and catalysts and after possible hydrogenation or hydrogenolysis in pretreatment reactors it is finally equipment and catalysts and after possible hydrogenation or hydrogenolysis in pretreatment routed to the catalytic reactor of aqueous phase reforming (APR) with a sugar concentration between 10 reactors it is finally routed to the catalytic reactor of aqueous phase reforming (APR) with a sugar and 15 wt% [125]. During APR the hydrolysate slurry reacts with water which converts the sugars and concentration between 10 and 15 wt% [125]. During APR the hydrolysate slurry reacts with water sugar alcohols into H , CO , lower saturated hydrocarbons, and condensable chemical intermediates at which converts the2suga2rs and sugar alcohols into H2, CO2, lower saturated hydrocarbons, and temperatures about 175–300 ◦C and pressures of 10–90 bar over supported metal or metal alloy catalysts condensable chemical intermediates at temperatures about 175–300 °C and pressures of 10–90 bar such as Pt or Ni-Sn [125–127]. The specific mixture composition depends on the reactor design, process over supported metal or metal alloy catalysts such as Pt or Ni-Sn [125–127]. The specific mixture conditions, feed concentration, solution pH, catalyst support and catalyst. The reactions involved composition depends on the reactor design, process conditions, feed concentration, solution pH, are considered to be (a) the reforming of the sugars which produces H , (b) the dehydrogenation catalyst support and catalyst. The reactions involved are considered to2 be a) the reforming of the of alcohols, (c) the hydrogenation of carbonyls, (d) deoxygenation reactions, (e) hydrogenolysis sugars which produces H2, b) the dehydrogenation of alcohols, c) the hydrogenation of carbonyls, d) and (f) cyclization. In situ generation of H from APR is considered of key importance for the deoxygenation reactions, e) hydrogenolysis a2nd f) cyclization. In situ generation of H2 from APR is de-functionalization of the very reactive carbohydrate to a less reactive mono-oxygenated species considered of key importance for the de-functionalization of the very reactive carbohydrate to a less (alcohol, ketone or aldehyde) which can then be converted into a non-oxygenated hydrocarbon through reactive mono-oxygenated species (alcohol, ketone or aldehyde) which can then be converted into a conventionalcatalyticcondensationandhydrotreatingtechniques[120].AnyexcessH isrecycledto non-oxygenated hydrocarbon through conventional catalytic condensation and 2 hydrotreating upgradetheaqueoussolutionofcomplexC andC sugarmixturesupstreamtheAPRreactorthrough techniques [120]. Any excess H2 is recycle5d to up6grade the aqueous solution of complex C5 and C6 the reactions of hydrogenation and hydrogenolysis. Hydrogenation takes place in the presence of sugar mixtures upstream the APR reactor through the reactions of hydrogenation and hydrogen at 100–150 ◦C and 10–30 bar causing the saturation of the C=C, C=O and C–O–C bonds hydrogenolysis. Hydrogenation takes place in the presence of hydrogen at 100–150 °C and 10–30 bar over metal catalysts such as Ru, Pt, Pd and Ni. Hydrogenolysis occurs in presence of hydrogen at causing the saturation of the C=C, C=O and C–O–C bonds over metal catalysts such as Ru, Pt, Pd and 125–230 ◦C and 14–300 bar causing the selective cleavage of C–C or C–O bonds of specific molecules Ni. Hydrogenolysis occurs in presence of hydrogen at 125–230 °C and 14–300 bar causing the like glycerol for the production of more valuable polyols or diols which are useful in the production of selective cleavage of C–C or C–O bonds of specific molecules like glycerol for the production of more valuable polyols or diols which are useful in the production of chemical polymers [128]. Hydrogenolysis takes place under alkaline conditions over supported metal catalysts such as Ru, Pd,PDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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